Alkali metal cation complexation by 1,3-alternate,mono-ionisable calix[4]arene-benzocrown-6 compounds

Alkali metal cation extraction behaviour for two series of 1,3-alternate, mono-ionisable calix[4]arene-benzocrown-6 compounds is examined. In Series 1, the proton-ionisable group (PIG) is a substituent on the benzo group of the polyether ring that directs it away from the crown ether cavity. In Series 2, the PIG is attached to one para position in the calixarene framework, thereby positioning it over the crown ether ring. Competitive solvent extraction of alkali metal cations from aqueous solutions into chloroform shows high Cs⁺ efficiency and selectivity. Single-species extraction pH profiles of Cs⁺ for Series 1 and 2 ligands with the same PIG are very similar. Thus, association of Cs⁺ with the calixcrown ring is more important than the position of the PIG relative to the crown ether cavity. Solid-state structures of two unionised ligands from Series 2 are presented. Also described is a crystal containing two different ionised ligand–Cs⁺ complexes.     

Ion-pair extraction of transition metal cations from aqueous media using novel N2O2-macrocyclic crown ligands

Three new macrocyclic crown ether ligands containing nitrogen–oxygen donor atoms were designed and synthesized from 1,4-bis(2′-formylphenyl)-1,4-dioxabutane and 4-nitro-o-phenylenediamine. Ion-pair extraction of metal picrates such as Ag⁺, Hg²⁺, Cd²⁺, Zn²⁺, Cu²⁺, Ni²⁺, Mn²⁺, Co²⁺, and Pb²⁺ from aqueous phase to the organic phase was carried out using the novel ligands. The solvent effect over the metal picrate extractions was investigated at 25 ± 0.1 °C by using UV–visible spectrometry. The extractability and the values of the extraction constants (log K_ex) were determined for the extracted complexes.     

Phosphorus-containing podands. 8. A study of metal-ligand interaction by fourier transform infrared spectroscopy in anhydrous acetonitrile

The interaction of phosphorus-containing monopodands with Li⁺, Na⁺, and K⁺ cations in anhydrous CH₃CN has been studied by FTIR spectroscopy. It has been shown that phosphoryl groups of the ligands take part in the formation of complexes with the alkali metal cation. The IR results obtained do not permit a clear conclusion as to whether or not the ether oxygen atoms of the ligand polyether chain participate in the complexation. It is suggested that in CH ₃ CN the formation of 1:1 complexes is not accompanied by conformational reorganization of the monopodand.Institute of Physiologically Active Substances, Russian Academy of Sciences, Chernogolovka 142432. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 884–889, April, 1992.     

Coordination Chemistry of Acrylamide. 6 Synthesis and Coordination Compounds of N‐Pyrazolylpropanamide – a Versatile Acrylamide‐derived Ligand

The syntheses, spectroscopy and single crystal X‐ray structures of the multifunctional acrylamide‐derived ligand N‐pyrazolylpropanamide (= L) ( 1 ), and its complexes [L₂CuCl₂] ( 2 ) and [L₄Co₃Cl₆] ( 3 ) with copper(II) and cobalt(II) chlorides, respectively, are described. The ligand 1 is easily obtained in one step by the reaction of pyrazole with acrylamide in a 1:1 molar ratio in the presence of trimethylbenzylammonium hydroxide as a basic catalyst. The reaction of CuCl₂·2H₂O with 1 in a 1:2 metal salt:ligand molar ratio in ethanol/‐triethylorthoformate solution gave coordination compound 2 . The crystal structure of 2 contains two seven‐membered chelate rings formed by two nitrogen atoms of the pyrazolyl groups and two weakly coordinated carbonyl oxygen atoms of the substituted amide moieties. Two chloride ions in the axial positions complete a distorted octahedral coordination environment around the Cu^II atom. The reaction of CoCl₂·6H₂O with 1 in a 1:2 metal salt:ligand molar ratio afforded the unusual zwitterionic complex 3 . The crystal structure of 3 contains a central cobalt atom in an octahedral coordination surrounded by four ligands in which two of them act as chelate ligands and the other two, coordinated via the carbonyl oxygen atoms of the amide moieties to this metal center, act as bridging ligands bonded to two CoCl₃^? units.     

The synthesis and characterization of 22-membered diazapentathia macrocycles and investigation of their ion extraction capability from aqueous media

Two new macrocyclic ligands, (5) and (6), containing nitrogen–sulfur donor atoms were designed and synthesized in a multi-step reaction sequence. Ion extraction capability of macrocycles (5) and (6) were investigated involving solvent extraction of metal picrates such as Ag⁺, Hg²⁺, Cd²⁺, Zn²⁺, Cu²⁺, Ni²⁺, Mn²⁺, Co²⁺ and Pb²⁺ from aqueous phase to the organic phase. The metal picrate extractions were carried out at 25 ± 0.1 °C and extractions were measured by u.v.–visible spectrometry. The extractability and selectivity of the mentioned metal picrates were evaluated depending on the organic solvents used for extraction. The extraction constant (log K_ex) and the complex composition of each metal complex were determined using spectroscopic methods.     

Synthesis of a fluorescent 14-crown-4 derivative bearing a proton-dissociable moiety and its use for selective lithium-ion extraction

The fluorescent 14-crown-4 derivative possesses a p-(1,8-naphthalenedicarboxi-mido) phenol moiety as the proton -dissociable fluorophore; its synthesis is described. Highly selective extraction of lithium is achieved with the crown ether, based on a proton/metal ion-exchange mechanism. Extraction is accompanied by significant changes in the absorption and fluorescence spectra of the organic phase. Extraction equilibrium constants for the lithium and sodium ions are evaluated, the Li⁺/Na⁺ selectivity ratio being 200; other alkali metal ions were not extracted. The Li⁺ extraction quenched the fluorescence intensity of the crown ether, in correlation with the initial cation concentration in the aqueous phase.     

Molecular Design of Calixarene 5. Syntheses and Cation Selectivities of Novel Schiff's Base p‐tert‐Butylcalix[4]arenes

Five novel Schiff's bases p‐tert‐butylcalix[4]arenes have been synthesized in high yields by the reaction of 1,3‐distally disubstituted p‐tert‐butylcalix[4]arene amine (1) with the corresponding aromatic aldehydes, and their cation binding abilities and selectivities with alkali and heavy metal ions have been evaluated by solvent extraction of aqueous metal picrates to show the highest Ag⁺ extractability for Schiff's base p‐tert‐butylcalix[4]arene (6) and the best Na⁺/Li⁺ and Ag⁺/Ti⁺ selectivities for Schiff's base p‐tert‐butylcalix[4]arene (4 and 2) over any other calix[4]arene derivatives, respectively.     

Synthesis and crystal structure of a two‐dimensional sodium coordination polymer of 4,4′‐(diazenediyl)bis(1H‐1,2,4‐triazol‐5‐one)

The crystal engineering of coordination polymers has aroused interest due to their structural versatility, unique properties and applications in different areas of science. The selection of appropriate ligands as building blocks is critical in order to afford a range of topologies. Alkali metal cations are known for their mainly ionic chemistry in aqueous media. Their coordination number varies depending on the size of the binding partners, and on the electrostatic interaction between the ligands and the metal ions. The two‐dimensional coordination polymer poly[tetra‐μ‐aqua‐[μ₄‐4,4′‐(diazenediyl)bis(5‐oxo‐1H‐1,2,4‐triazolido)]disodium(I)], [Na₂(C₄H₂N₈O₂)(H₂O)₄]_n, (I), was synthesized from 4‐amino‐1H‐1,2,4‐triazol‐5(4H)‐one (ATO) and its single‐crystal structure determined. The mid‐point of the imino N=N bond of the 4,4′‐(diazenediyl)bis(5‐oxo‐1H‐1,2,4‐triazolide) (ZTO²⁻) ligand is located on an inversion centre. The asymmetric unit consists of one Na⁺ cation, half a bridging ZTO²⁻ ligand and two bridging water ligands. Each Na⁺ cation is coordinated in a trigonal antiprismatic fashion by six O atoms, i.e. two from two ZTO²⁻ ligands and the remaining four from bridging water ligands. The Na⁺ cation is located near a glide plane, thus the two bridging O atoms from the two coordinating ZTO²⁻ ligands are on adjacent apices of the trigonal antiprism, rather than being in an anti configuration. All water and ZTO²⁻ ligands act as bridging ligands between metal centres. Each Na⁺ metal centre is bridged to a neigbouring Na⁺ cation by two water molecules to give a one‐dimensional [Na(H₂O)₂]_n chain. The organic ZTO²⁻ ligand, an O atom of which also bridges the same pair of Na⁺ cations, then crosslinks these [Na(H₂O)₂]_n chains to form two‐dimensional sheets. The two‐dimensional sheets are further connected by intermolecular hydrogen bonds, giving rise to a stabile hydrogen‐bonded network.     

Synthesis,crystal structure and silver complexation of a novel saddle-shaped stilbenophane: NMR and theoretical study on the complex

A new Z,Z-stilbenophane was synthesised and characterised. According to an X-ray structure analysis, the structure has a saddle shape, with the π-electrons of the double bonds and the oxygen atoms pointing towards the centre of a cavity. The ligand forms a 1:1 complex with Ag⁺. Both NMR spectra and theoretical analysis (Gauge-independent atomic orbitals (GIAO) and Quantum theory of atoms in molecules (QTAIM)) suggest that the silver cation is bound within the molecular cavity. The metal is coordinated by the two olefinic double bonds and the four oxygen atoms in an approximately octahedral environment. The coordination motif is unusual because the soft silver cation prefers the interaction with the four hard oxygen atoms over the bonding to the arene units, which is frequently observed in Ag⁺ arene complexes.     

The Synthesis and Investigation of Liquid-Liquid Extraction Capability of N-Diphenylphosphino-N-ethylaniline and Its Chalcogenide Derivatives

The aminophosphine ligand was synthesized by the reaction of N-ethylaniline with chlorodiphenylphosphine in the presence of triethylamine at low temperature. Oxidation of the ligand with elemental sulfur or selenium afforded the corresponding aminophosphine sulfide and selenide. The compounds were characterized by elemental analyses, IR, ¹H and ³¹P NMR. N-diphenylphosphino-N-ethylaniline and its chalcogen derivatives were used as ligands in solvent extraction of metal picrates such as Cd²⁺ and Ni²⁺ from the aqueous to the organic phase. Influences of parameters such as pH of the aqueous phase, solvent, extraction time, and extradant concentration were investigated to determine the extraction ability of ligands for metal ions. Results of the experiments showed that an extractability of 95.5 and 97.8%, respectively for Ni²⁺, and Cd²⁺ at pH 2 could be achieved.

     

Untersuchung der Komplexierung von Na+, K+, Ca2+ und Ba2+ mit einigen elektrisch neutralen Liganden durch Messung von 13C-chemischen Verschiebungen und Spin-Gitter-Relaxationszeiten

Investigation of the complexing of Na⁺, K⁺, Ca²⁺ and Ba²⁺ with some uncharged ligands by ¹³C-chemical shift and spin-lattice relaxation time measurements The influence of Na⁺, K⁺, Ca²⁺ and Ba²⁺ ions on ¹³C chemical shifts and on spin-lattice relaxation times of some electrically neutral ion carriers was investigated. In the solvents CD₃CN and CD₃OD and in presence of an excess of metal ions ligand 4 (see the Scheme) forms complexes of 1:1 stoichiometry. All four oxygen atoms of the ligand as well as solvent molecules take part in the coordination. In CDCl₃ as solvent, for all ions investigated except sodium, only 1:2 complexes (metal/ligand) were observed with 4 . Sodium ions form both 1:1 and 1:2 complexes in this solvent. In the 1:2 complexes of the investigated monovalent ions only one, in those of the divalent ions both amide carbonyl groups of ligand 4 take part in the coordination.     

Spectroscopic and Electrochemical Studies of Transition Metal Complexes with N,N′-Bis(2-aminothiophenol)-1,7-bis(2-formylphenyl)-1,4,7-trioxaheptane and Structure Effects on Extractability of Ligand towards some Divalent Cations

Summary. La(III), Cu(II), Ni(II), and Zn(II) metal complexes with a novel quadridentate Schiff base derived from 1,7-bis(2-formylphenyl)-1,4,7-trioxaheptane and 2-aminothiophenol were synthesized and characterized by microanalytical data, elemental analysis, magnetic measurements, ¹H NMR, ¹³C NMR, UV-Vis, IR, mass spectra, cyclic voltammetric and conductance measurements. The extractability of divalent cations was evaluated as a function of relationship between distribution ratio of the metal and pH or ligand concentration. The highest extraction percentage of Cu²⁺ and Ni²⁺ showed pH 7.0 and 6.4. It was concluded that the ligand can effectively be used in solvent extraction of copper(II) and nickel(II) from the aqueous phase to the organic phase.     

Spectroscopic and extraction studies of new transition metal complexes with N,N ′- bis (2-aminothiophenol)-1, 4- bis (2-carboxaldehydephenoxy)butane

Metal complexes of La(III), Cu(II) and Ni(II) with a thio Schiff base derived from 1,4-bis(2-carboxaldehydephenoxy)butane and 2-aminothiophenol have been synthesized in absolute ethanol and characterized by microanalytical data, magnetic measurements, ¹H NMR, ¹³C NMR, UV-visible, IR-spectra, mass spectra and conductance measurements. The extractability of divalent cations was evaluated as a function of relationship between distribution ratios of the metal and pH or ligand concentration. The highest extraction percentage of Cu⁺² and Ni⁺² were at pH 7.0 and 6.4, respectively. The ligand can effectively be used in solvent extraction of copper(II) and nickel(II) from aqueous phase to organic phase.     

Influence of O/S/Se Exchange on the Stability of 1,3,4-Selana(Thia/Oxa)Diazole-Palladium Complexes as Studied by Electrospray Ionization Mass Spectrometry

Abstract

The complexes of 2-phenyl-1,3,4-selena(thia/oxa)diazole with a palladium cation were studied by using electrospray ionization mass spectrometry. Palladium chloride was used as a source of palladium cations. The complexes of ligand:metal stoichiometry of 3:1 (ions [L₃+PdCl]⁺) were formed for selenadiazoles and thiadiazoles. Quantum mechanical calculations performed indicated that ligand molecules are attached to palladium cation by the N-4 atom. The fragment ions formed [L₂–H+Pd]⁺ may be regarded as organometallic species. Selenadiazoles were found more prone to form the palladium complexes than thiadiazoles. Oxadiazoles did not yield the respective palladium complexes. For comparison, the nickel cation was also included in the study but only 1:1, and less abundant 2:1 complexes were observed. Exchange of selenium into oxygen does not affect the abilities of the ligands to form nickel complexes.     

Analysis of Equilibria in the Extraction of Cesium Nitrate by Calix[4]arene-bis(t-Octylbenzo- Crown-6) in 1,2-Dichloroethane

The extraction of CsNO₃ by the highly lipophilic calixarene-crown ether calix[4]arene-bis(t-octylbenzo-crown-6) (CABOBC6) in 1,2-dichloroethane (1,2-DCE) at 25 °C has been shown to be consistent with the formation of both 1 : 1 and 2 : 1 metal : ligand species. Variation of the aqueous-phase CsNO concentration up to 1.0 M and variation of the organic-phase calixarene concentration up to 0.10M was modeled by the program SXLSQI. Formation of the organic-phase species CsBNO₃ (B = calixarene) was confirmed as well as the organic-phase dissociation products CsB⁺ and NO₃ ^-. Good evidence for the 2 : 1 metal : ligand organic-phase species Cs₂B(NO₃)₂ was also found, although the dissociation of nitrate from this complex was not observed. Binding of the second Cs⁺ cation by the ligand is approximately two orders of magnitude weaker than binding of the first Cs⁺ cation. The logarithm of the apparent partition ratio (log P_B) of the calixarene between water and 1,2-DCE was found by ¹H-NMR techniques to be > 5.1.     

Complexes of Di‐ and Triazacrown Ethers with Heavy Metal Ions in Water Solution

This research concerns the analysis of the metal ion binding of benzo‐ and pyridine‐azacrown ether compounds of different structures and sizes by potentiometric method. The ligands are able to form 1 : 1 complexes with heavy metal ions (Cu⁺², Pb⁺², Cd⁺², Ag⁺, Ni⁺², Zn⁺²) in water of middle or high stability. To understand the selectivity in cation binding, different factors were considered.     

NMR study of the coordinating behavior of 2,6‐bis(benzimidazol‐2′‐yl)pyridine

The coordination sites of 2,6‐bis(benzimidazol‐2′‐yl)pyridine ( 1 ) toward protons and the diamagnetic metal ions Li⁺, Na⁺, and Co³⁺ were investigated by NMR spectroscopy. Variable temperature ¹H and ¹³C NMR experiments were performed on 1 in order to evaluate the tautomeric equilibrium and hydrogen bonding. Imidazole dicoordinated aromatic nitrogen atoms were protonated by trichloroacetic acid and the three N‐dicoordinated atoms by fuming H₂SO₄. Reactions of the ligand 1 and benzimidazole 2 with metallic sodium or LiH afforded anionic species; the alkali metal ions appeared solvated by THF, but not by the ligands 1 or 2 . In contrast, reaction of 1 with Co(III) produces the stable cation [Co( 1 ‐H)₂]⁺ with cobalt ion coordinated by two molecules of the monodeprotonated ligand. © 2000 John Wiley & Sons, Inc. Heteroatom Chem 11:392–398, 2000     

The Chemistry of Separations Ligand Degradation by Organic Radical Cations

Solvent based extractions of used nuclear fuel use designer ligands in an organic phase extracting ligand complexed metal ions from an acidic aqueous phase. These extractions will be performed in highly radioactive environments, and the radiation chemistry of all these complexants and their diluents will play a major role in determining extraction efficiency, separation factors, and solvent-recycle longevity. Although there has been considerable effort in investigating ligand damage occurring in acidic water radiolysis conditions, only minimal fundamental kinetic and mechanistic data has been reported for the degradation of extraction ligands in the organic phase. Extraction solvent phases typically use normal alkanes such as dodecane, TPH, and kerosene as diluents. The radiolysis of such diluents produce a mixture of radical cations (R^•+), carbon-centered radicals (R^•), solvated electrons, and molecular products such as hydrogen. Typically, the radical species will preferentially react with the dissolved oxygen present to produce relatively inert peroxyl radicals. This isolates the alkane radical cation species, R^•+ as the major radiolytically-induced organic species that can react with, and degrade, extraction agents in this phase. Here we report on our recent studies of organic radical cation reactions with various ligands. Elucidating these parameters, and combining them with the known acidic aqueous phase chemistry, will allow a full, fundamental, understanding of the impact of radiation on solvent extraction based separation processes to be achieved.     

Synthesis,Crystal Structure and Characterization of Polynuclear Potassium(I), Copper(II) and Cobalt(II) Complex with Acetylacetonethylenediamine

The title complex [K{Cu(acen)}₃]₂[Co(NCS)₄]·1/4CH₃OH (acen = acetylacetonethylenediamine anion) has been prepared and characterized. Single-crystal x-ray analysis reveals that the complex crystallizes in space group P I with a = 11.442(2), b = 15.098(3), c = 28.500(4) Å, α = 82.77(1), β = 83.58(1), γ = 85.07(1)°. The crystal consists of the complex [K{Cu(acen)}₃]⁺ cations, [Co(NCS)₄]^2? anions and methanol molecules. Three [Cu(acen)] molecules function as bridging ligands through phenolic O atoms to one K⁺ to give the tetranuclear [K{Cu(acen)}₃]⁺ cation. Each copper(II) atom in the cation is in a square-planar geometry, being coordinated by two oxygen atoms and two nitrogen atoms from a quadridentate acen ligand. The cobalt(II) atom is coordinated by four nitrogen atoms of thiocyanate ligands, forming a deformed tetrahedral environment. The IR and UV-Vis spectra have also been investigated.     

Theoretical study on the complexation of the cesium cation with dibenzo-18-crown-6

Abstract  

By using quantum mechanical calculations, the most probable structures of free dibenzo-18-crown-6 ligand and the cationic complex species of Cs⁺ both with one and with two dibenzo-18-crown-6 ligands were derived. In these two complexes, the “central” cation Cs⁺ is bound by strong bond interactions to the corresponding ethereal oxygen atoms of the parent crown ligand.